Manufacture of amines



Patented Aug- 22, 1939v I "UNITED s'rA'ras 2,170,111 MANUFACTURE or humus Herman A. Bruson, Philadelphia, Pa, lillhfll' to Riihm & Haas Company, Philadelphia, Pa.

' No Drawlng.- Application Serial No. 82,1

' 15 Claims. 260-293)- This invention relates-to new amines and their salts and to the quaternary ammonium bases and salts derived from these amines. It also relates to a process for preparing these new compounds. It relates more particularly to the water-soluble salts and bases which have been found to be excellent wetting, emulsify dispersing and cleaning agents which may be generally classed as capillary active compounds.

The amines are those having the general structure in which R is a hydrocarbon radical containing an aromatic nucleus at its point of attachment to the ether oxygen atom, A is an alkylene radical having more than one carbon atom,.n is equal to one (1) or zero (0) and N is the nitrogen atom derived from ammonia, a. primary or secondary aliphatic, cycloaliphatic, arylaliphatic or hydroxyaliphatic amine or secondary heterocyclic amine.

These amines arereadily prepared by condensing one mol each of a monohydric phenol and a polyalkylene ether, having a halogen substituent on each of its terminal carbon atoms, in the presence of an alkaline condensing agent, reacting the product thus obtained with ammonia, a primary or secondary amine and treating the resulting amine hydrohalide with an alkali or alkaline earth hydroxide.

The reactions involved may be outlined -as' follows:

in which X is a halogen atom.

with an alkylating agent such as an alkyl chlo- Quaternary ammonium salts corresponding to these amines may be made by treating a tertiary amine having as a substituent the radical ride, dialkyl sulfate, aralkyl chloride, etc. Alternatively the quaternary ammonium salts may be obtained by treating a tertiary amine with the phenolic complex ether chloride. The bases maybe obtained from these salts by treatment with caustic.

In preparing the complex ether halide as in 5 Equation (1) a monohydric phenol is treated with at least an equimolecular quantity of a dihalogeno ether in which each of the halogen atoms is attached to a terminal methylene group, in the presence of at least an equimolecular proportion of an alkali hydroxide. This mixture is heated at about 100 to 140 C. until the reaction is complete. The time of heating may" vary from two to more than fifteen hours, depending on the reactants. Thetemperature at which the reaction is carried out will also vary somewhat according to the actual materials involved. when the reaction is complete, the alkali halide is filtered off. The product is usually a liquid of relatively high boiling pointwhich may be purified by distillation in vacuo.

In order to prepare the amine or quaternary ammonium salt this halogenated complex ether is heated with ammonia or the desired primary,

secondary or tertiary amine until the reaction is complete. This usually requires from about one to fifteen or more hours at temperatures ranging from about 75 to about 180 C. depending on the nature and reactivity of the ingredients. The product is then treated with an alkali hydroxide to set free the base which may be sepa-v rated from the aqueous solution and purified by distillation in vacuo. In many cases reaction products may be used directly since, as salts of the amines or of the quaternary ammonium bases, they are soluble in water. The free base may then be' converted to a salt by treatment with an organic or inorganic acid such as, for example, acetic, formic, lactic, acrylic, propionic,

- crotonic, phosphoric, sulfuric, hydrochloric, etc. 40

In case it is desired to convert the amine to a quaternary ammonium compound, it may be treated with an alkvlating or aralkylating agent such as benzyl chloride, dimethyl sulfate, diethyl sulfate, dimethyl oxalate, methallyl chloride, 5 methyl iodide, ethyl bromide, methyl thiocyanate, benzyl thiocyanate' and other similar ones The phenols which can, be used for the purpose of this invention include the following: phenol, 0-, m-, or p-cresol, thymol, carvacrol, p-ter-bu- 5 tylphenol, p-sec-butylphenol, p-ter-amylphenol, p-n-amylphenol, n-amyl-m-cre'sol, *p-sec-octylphenol, p-ter-octylphen'ol, p-sec-hexylphenol, laurylphenol, o-, m-, or-D-cyclohxylphenol, o-,

m-, or p-phenylphenol, 0- or p-benzylphenol, a- I inclusive since these compounds show the h and lathery when shaken; Such solutions can est degree of c pil ary v y- The alkyl ro p be used for wetting out metal surfaces as in the may be a straight or branched chain. cleaning of steel automobile bodies with phos- Among the dihalogeno-polyalkylene ethers phoric acid or for rustproofing steel with metal which can be used may be mentioned p,p'-dichlophosphate-phosphoric acid solutions. m

ro-diethyl ether, p,p'-dichloro-diisopropyl ether. E 2 dichloro-dibutylether, dichlorodiamyl ether, and mmple v on. on, cinl /cH:-CH:0H

0H.-d--cH,- :-C 'ocmcu,o-cn,cmrz (g a: 15

H1 HI ciHi0,s0,-o CHrCHgOH th corresponding dibromo derivatives, p-chloro- A solution of 30 grams of p-(d,c,-y,-y-tetraethyl -B'- chloroethoxyethyl ether, and their methylbutyl) phenoxyethoxyethyl-diethanolamine higher homologues containing up to 18 carbon in 50 grams of toluene was mixed with a solu- 20 atoms. tion of 12.5 grams of diethylsulfate in grams 20 The compounds used for the amination of the of toluene, and the mixture heated for one hour at monohalogeno-polyalkylene ethers of the phe- 80-85 C. The clear solution obtained was then nols used can be ammonia or primary, secondary evaporated under reduced pressure at 40-50 C.

5 and tertiary amines. Typical useful amines for to remove the toluene. The residual quaternary 2 the purpose are mono-, di-, or trimethylamine, ammonium compound was a viscous amber- 25 mono-, di-, or triethylamine, or their highcolored oil which dissolved readily in water to er homologues; monoethanolamine, diethanolgive a clear, foamy, soapy solution, useful as a amine, dibenzylamine, cyclohexylamine, dicyclowetting-out agent and which was stable to hard hexylamine, piperidine, morpholine, benzyl-diwater. The quaternary ammonium base can be methylamine, and the like. 7 liberated by treatment with alcoholic potassium 30 For practical purposes and in view of their hydroxide. cheapness, p,p'-dichlorodiethyl ether and p,p'- Example 3 CH3 CH1 /CH:CH3 cnr-e-cn,-e oomcmo cm-cnr-n 0 35 lHa all: CHPCH:

dichloro-diisopropyl ether are preferred for illus A mixtureof 25 grams of morphonne and 62 trating this invention in the following examples.- eo-rne invention, however, is notlimited to the 5: 3? i ggli' z fi fig a 4o exact conditions of time, temperature, concenf y t 10042 0 er tration etc. shown nor to the exact ingredients as 7 ours a o W it may be otherwise practiced within the scope of I was made with caustic soda 5011mm! and the appended claims. the oil layer separated and washed. Upon frac- 'Emmple1 tionatingthisoilinvacuoanwityieldofa om cm cm-cmon oH= :1-omo- -o-cmcmocn,-cm1 CH: (3H5 CHr-OHaOH 0 A mixture of 103 grams of p-(d,,- ,'y-tetramethylbutyl) phenol, 22 grams of sodium hydroxf 'ff ggggff gi g m m ide, 20 cc. of water and 286 grams of p,p'- b0 Z as a pale y dichlorodiethyl ether was heated under a reflux dissolved re 1 a of -condenser at -120 C. for 6 hours while so u (ms 55.

surfing continuousm The sodium chloride phosphoric, oxalic, or acetic acids, and these soluformed was filtered oil" and the p-(,a,'y,'y-tetraf f g gz 23 when methylbutyDphenoxyethoxy-ethyl chloride. p0 g grams ,0 -cm-owmn-crn-c(cn, 0 -cHrcn,o-omcmc1 so boiling at 177-1'78 0/4 mm. was isolated as a methylbutyl) phenoxyethoxy-ethyl-N-morpholine colorless oil by distillation of the filtrate in vacuo. with 16 grams of 'diethyl sulfate in toluene as A mixture of 39 grams of the p-(e,d-,'y,'y-tetradescribed in Example 2, the corresponding com- 65 methylbutyl) -phenoiwethoxy-ethyl chloride thus pound as obtained and 26 grams of diethanolamine was heated for 15% hours on an oil bath at -135 C. under a reflux condenser while stirring. The cimOo-cnronro-cnrcnrn 0 thick brown oil obtained was mixed with so cc. of warms CHTGH/ '10 -10% caustic soda solution, 100 cc. of water and 7o- 2 or p-naphthol, ter-butyl-p-naphthol, ter-octylp-naphthol, 1,3,5-xylenol, and their obvious equivalents. The most useful products are those derived from p-alkylated phenolsin which-the alkyl group contains from 4 to 12 carbon atoms cc. toluene and warmed for one-half hour on a water bath at 60-70" C. The toluene layer was then separated and washed with 100 cc. of water.

methylbutyl) phenoxyethoxyethylediethanolamine was obtained as a pale yellow viscous oil in a yield of 82% of theory. It boiled at 255-260 0/5 mm.

This all when dissolved in 10% phosphoric acid gave a clear solution which was very foamy, soapy,

was obtained. It is a viscous, pale yellow mass which dissolves readily in water to give a foamy, soapy solution. The quaternary ammonium base After distillation of the toluene and fractionation 75 of the residual oil in vacuo. the p-(a, d,'y,- -tetracan be liberated by treatment with alcoholic barium hydroxide solution.

mixture of 52 grams of p-( ag -tetramethylbutyDphenoxyethoxy-ethyl chloride with 25 rams of diethylamine under reflux for 9 hours on a boiling water bath. The base was liberated with dilute caustic soda solution. It separated as a yellowish oil boiling at 210-220 C/10' mm. Upon treatment with dimethyl sulfate it gave a water-soluble, soap-like body having the formula The analogous diamylamine derivative obtained from, technical diamylamine and p-(a,a,'y,'y-

tetramethylbutyl)phenoxyethoiw-ethyl chloride boiled at 220-240 C/6 mm. Its phosphate gave a very foamy solution in water.

Example 6 CH1 cm-cmon H;- OO-CHrCHrO-Cllz-CHz-N H1 CHz-CHzOH is a pale yellow oil boiling at 265 C/ mm.

ride having the above formula. Its aqueous solution is foamy and soap-like and may be used as a penetrating agent. The corresponding quaternary ammonium hydroxide is formed by treatment with alcoholic sodium hydroxide solution.

Example 9 on, CHz-CHgOH cm-onz-o-Oo-onrcnro-om-onrn V I HI CHrCHgOH .31 grams of 'diethanolaminejwas mixed with 54 grams of p-ter-amylphenoxyethoxy-ethyl chloride, a colorless oil boiling at 153-155 0/3 mm. which was prepared from p-ter-amyl phenol,

molecuiarly equivalent quantity of diethyl suifate as described in Example-2, the p-ter-amylphenoxyethoxyethyl-dihydroxydiethyl-ethyl ammonium sulfuric ethyl ester CzHs CIHrO- 8 03-0 CHI-C3101! 2,170,111 3 Example 4 ca, din cm-cm cin-d-cm--Oo-cm-cmw-cm-cHr-N om 6 47H: CHr-CH: I

This compound was prepared by heating 'a The acetate, phosphate, and lactate of this mixture of 62.5 grams of p-(a,a,-y,-y-tetramethylbase dissolve in water to give foamy solutions butyDphenoxyethoxy-ethyl chloride with .17 having low surface tensions. The quaternary grams of piperidine at 130-140? C. for 10 hours, ammonium compounds derived from the above 1'0 liberating the base with caustic soda, and fracbase and diethyl sulfate, dimethyl sulfate, or

tionating in vacuo, as described in Example 3. benzyl chloride are water-soluble capillary active The compound was obtained in an 80% yield, as compounds. 7 a yellow oil boiling at 185-200 C/l mm., which Example 7 upon cooling solidified to a waxy. crystalline masm on; CH1\ om It dissolved readily in 10% phosphoric acid to CHrCIL-(J-OO-CHrQHi-OCHrCIh-N form a soap-like, foamy solution.

One molecular equivalent of the above amine in an equal volume of benzene was mixed with A mixture 01 grams 0 P-ter-amylphemxy' one molecular equivalent of benzyl chloride. The .ethoxyethyl .chlm'ide and grams or mixture was warmed 1 hour at 75? C. and the methylamine was heated in j tube at benzene ofl under reduced pressure C. for 2 hours. 18 crystalline 111855 01)- The residue f p (a,a,7,.y tetramethy]buty1) tained after evaporation of the'excess trimethylphenoxyethoxy N IS the quaternary ammonium chloride chloride is useful as a spreader for insecticides. hfwmg the above formula- Its N m The quaternary ammonium base is nbemted by y elds a stable heavy foam and is useful for fixing treatment with alcoholic caustic soda solution. dlfect dyestufis on F fibre- Upon treatment By substituting u u butyl phenoxy with alcoholic potassium hydroxide the quaterethoxyethyl chloride for the p-tertiary octyl comnary ammomum hydroxlde is formedpound in the foregoing example, the N-p-tertiary Example 8 I butyl phenoxyethoxyethyl piperidine is formed E assaults; sszszizrat 0 Example 5 OH; 01

on; EH1 01H- A mixture of 20.8 grams of p-ter-butylphen- CH CH (Hm on N oxyethoxy-ethyl chloride and 11 grams of benzyl l L r r dimethylaniiue was heated under a reflux condenser for 2 hours at 150 C. The clear, viscous m s, c p was Prepared by heating a mass obtained is the quaternary ammonium chlo- 4. amour;

was obtained as a pale yellow oil. Its aqueous lar equivalent of methyl sulfate, the watersolution is slntahle as a wow: agent for soluble quaternary ammonium salt was. obcotton tained having cation active properties. It readily Enamels 1o combines with Gongo red dye to form an'insolu-' A mixture of 1 mol equivalent eam-tetra ole lake and is useful for improving the fastness, T methylbutylphenoxyethoxy-ethyl chloride and 2 to washing of direct dyes. mols (excess) of dlmethylamlne was heated in Exampze 13 an autoclave 5 hours at no" G. The reaction 35 was made alkaline with caustic soda som OH tion and the free-base isolated by distillation in I mode after removal oi unrescted ethy a. n1 1. e. QCHaro-CH:*CH:-N It was a colorless oil boiling at Isl-134 6/3 CHrCHOH This oil was heated with a molecularly equlvaf g l w lent quantity of dlethyl sulfiate in dry benzene Y on a water bath 1 hour Upon evaporation 41.5 grams of diethaholaminewas mixed with the solvent the ter'ocwlphenomethowethyx 51.5 grams of thymoxyethoxy-ethyl chloride, 9. methyleml mmmum ethyl Sulfate was lei; colorless oil boiling at 176-178 0110mm, which as a thick syrup. Its aqueous solution possesses was prepared from thymol, caustic Soda. and. 25. a 5? am is useful fixing p,fi'-dichlorodiethyl ether, according to the pro-' d dyes m cedure set forth in Example 1. The mixture was By substituting p'temary amyl phenoxye heated hours at 110-130 C., then made alka-' ethyl chloride for the p-tertiary octyl compound line; and the base which Separated as an an lithe g g 5:1 the g was washed and fractionated in vacuo. The- .oxye hyl e mamme h thymoxyethoxy-ethyldiethanolamm' e distilled atpared Ems can be-convemd e 233-236" 0/5 mm. as a pale yellow oil. Yield responding quaternary ammonium compounds. 72% of them? Example l1 1 Its phosphoric acid salt dissolved readily in'- CH3 CH3 z I on CHr'CuHi A mixture of 32 grams of p-(a,,7,7-tetrawater to given foamy solution usefulasawetting 40- methylbutyhphenoxyethoxy ethyl dim'ethybagent, My

amine and 12.7 parts of benzyl chloride was The analogous derivative obtained from xylenwarmed to C. with 50 grams of benzene for 2 oxy-ethoxy-ethyl chloride, a'colorless oil boiling hours. The benzene was then evaporated. The at 168 C/ 10 mm. which was prepared from 1,3,5- residual viscous mass gave a foamy, soapy soluxylenol, caustic soda and 3,5'-dichloro-diethyl tioninwater. ether according to the procedure set forth for g Example 12 Example 1, and diethanolamine, was a pale yellow v cm cnrc(cn=),-or1rc(cno o-cm-cn-o-on-cm-r t Ea on; 1 cm I 'SO1OCH: A mixture of 51.5 grams of p-(a,a,'y,'y-tetl'aoil boiling at 252 0/10 mm., the hydrochloride of methylbutyl) phenol, 11.7 grams of sodium hywhich possesses capillary active properties. 'droxide 20 cc. of water and 171 grams of fi,fi'- dichloro-diisopropyletherwasheatedat110-120 Example 14 a C. with rapid agitation under a reflux condenser A mixtureof 12.3 grams of a,a ,-y-tetramethylfor 9 hours. The product was worked up as in hutylphenol, 2.7 grams of caustic soda, 5 cc. of

Example 1, yielding 50 grams 0! ter-octylwater and 64 grams of fi-chloroethyl-p chlorp. fis phenoxyisopropow-isopropyl chloride. (Golorethoxyethyl ether, a colorless oil boiling at 235 (3.,

less oil B. li ido-195 C/5 mm.) prepared by treating triethylene glycol in dl-.

This oil was converted to the tertiary amine methylaniline with thionyl chloride, was heated 5 salt by heating it with excess of dimethylami'ne hours at -115". .C; while stirring under a. reflux at -140? C. in an autoclave for 2 hours. The condenser, The water was then distilled oil, the l 70 ;product was treated with excess caustic soda sosodium chloride removed by filtration and the 70;

lution and the free base isolated by distillation clear .filtrate 'fractlonated. The fiber-cotylunder reduced pressure. It formed a colorless phenoxyethoxy) ethyl-p-chloroethyl ether disoil boiling at 200 C/3 mm. Yield 70% of tilled as a colorless oil 9.11199-20'7 C/3 mm. This theory. was mixedrwith a molecularly equivalent quantity v 15;; Upon treatment 01; this base with one molecllofdiethanolaniine and heated 8 at 120: C'. :1

The base was then liberated by treatment with caustic soda. Its phosphate dissolves readily in water to give a foamy, soapy solution. Upon treatment with diethyl sulfate the water-soluble quaternary ammonium derivative is formed. Its aqueous solution is useful as. a wetting-out agent.

In place of the diethanola'mine, one can use diethylamine, piperidine, morpholine, dicyclohexylamine or dibenzylamine in the above condensation to obtain the analogous tertiary amines. The water-soluble phosphates, lactates, acetates, and quaternary ammonium salts of these phenol ethers are likewise useful as capillary active compounds.

' "Example 15 A mixture of 55 grams of p-teramylphenoxyon. I 1 om-ra-ong-a-O-o-om-omo-om-cm-M H: CH:

ethoxy ethyl chloride and 7 grams of anhydrous With diethanolamine and- Product obtained BQB-naphthoxy) ethyl-fi'-c h l o r o ethyl ether (from B-naphthol). B. P. 2l52l6/10 mm.

fl-(o-beuzylphenoxy) ethyl-W-ehlo roethyl ether (from o-benzol phe- B-(ocyclohexylphenoxy) ethyl-B'- chloroethyl other (from ocyclohexylphenol) B. P. roam 1o mm.

B (p-cyclohexylphenoxy) ethyl-,6-

cliloroehtggllether (from p-cyL-lo B (o-phenylphenoxy). ethyl-B-chleroethyl other (from o-phenyl- B (p-phenylphenoxy) ethyl-d chloroethyl ether (from p-phenylphenol). B. P. l-189/0.5 mm. M. P. 51.

fl Naphthoxyethoxyethyl-diethanolamine. Oil. B. P. 275-280/7 mm.

0 Benzylphenoxyethoxy ethyl diethanolamine. Oil. B. P. 280-285/6mm.

o Cyclohexylphenoxyethoxyethyl-diethanolamine.

Oil. B. P. 262l8 mm.

p cyclohexylphenoxyethoxyeth -diethanolamine. Oil. B. P. 280285/8 mm.

o-Phenylphenoxyethoxyethyldiethanolamine. Oil. B. P. 275280/l0 mm.

p-Phenylphenoxyethoxyethyldiethanolamine. (Resinous mass.)

With dibenzylamine and- Product obtained p ter octylphenoxyethoxyethyl N dibenzylamine. (W a? rystals.)

The water-soluble pentavalent N-derivatives of the above bases notably. their laotates, phosphates, acetates and the quaternary ammonium salts obtained with benzyl chloride, di'ethylsulfate, or dimethyl sulfate are likewise useful as capillary active agents,

Among the uses suggested for such capillary active compounds is their employment as textile assistants in dyeing, bleaching, mercerizing and mordanting operations; as spreaders for insecticides, dispersing agents for pigments, as wetting and penetrating agents, pickling inhibitors, and assistants in leather tanning and finishing operations. The water-soluble quaternary ammonium salts of the type herein set forth are particularly useful for rendering dyeings with acid, direct, or chrome dyestuifs on rayon, cotton, or on cellulose esters or ethers, faster to light and washings. For this purpose the textile is treated with a solution of the capillary active compound and subsequently dyed in the usual manner. The quaternary ammonium hydroxidesare useful as capillary active compounds in alkaline solution and may be used as mercerizing assistants.

I claim: 1. A compound having the formula CHr-CHQOH GHH-CHzOH 2. A compound having the formula E CHz-CHrE-C OCH-CHr-O-CHr-CHrN\ 4 H: I 3. A compound having the formula cm 1 om-om cHro-O-moHrom-o-orrrom-N om H: carom 4. A compound having the formula 0 xOo-onr-onr-o-om onen b in which X is an alkyl radical containing from four to twelve carbon atoms inclusive, and a and b are lower hydroxy alkyl radicals. Y

6. A compound having the formula in which X an alkyl radical containing from four to twelve carbon atoms and Y is a member of the group consisting of the methylene group and oxygen. y

7. A compound having the formula x in which X is an alkyl radical, a and b are lower alkyl radicals and n is aninteger less than 3.

8. A compound having the formula X x b in which X is an alkyl radical, a and b are lower hydroxy alkyl radicals and n is an in teger less than 3.

9. A compound having the formula on.or'r,

x cal-on in which X is an am! radical. Y is a member of the group consisting oi the methylene group and oxygen and an is an integer less than 3.

10. A compound oi the formula in which X is an alkyl radical, R is a member or the group consisting of benzene end naphthalene nuclei, A represents lower allwlene radicals con taming more than one carbon atom, a is an in teeer less than 3, and a and h are lower allsyl radicals.

11. A compound of the to o in which X is an alkyl radical, R is a mom-her oi the group consisting of. benzene and naphthalene nuclei, A represents lower alkylene radicals containing more than one carbon atom, '12 is an in teger less than 3, and a and b are lower hydrogzy aml radicals. l

12. A compound having the forums? is an integer less than 3,

arcane fin-1; more than one carbon ato n is an in teeer less t 3, and

is selected from the group oi NH2, 32 wow one] secondary lower alkyl, -lowr alkylol, oyclol, and aralisyl amine radicals and saturated heterocyclio radicals. id. as on; havlnethe seneialiormulais one Ween: swee r dic l. 01 the r u coins of radio 02 the benzene and naphthalene series, it represents lower alkylene radiconteininr; more than one carbon atom, 12

and

is selected from the group consistin of NHZ,

primary and secondary lower alkyl, lower alkyloL,

cycloalkyl, and aralkyl amine radicals and saturated heterocycllc amine radicals.

15. An amine having the-general formula- R-(0-A).0 -AN in which R is a hydrocarbon radical of the group consisting of radicals. of the benzene and naph-.

thalene series, A represents lower alkylene radicals containing more than one carbon atom, n is.

an integer less than 3, and

is selected from the group consisting 01' KHz, primary and secondary lower alkyl, lower alkylol,

in which X is an alkyl radical, R is a member'of the group consisting of benzene and naphthalene nuclei, A represents loweralkylene radicals concycloalkyl and arallwl amine radicals and saturated heterocyclic amine radicals. HERMAN A. BRUSON. 

